Process of treating crude oil having tar and asphalt content



Jan. 13, 1931. w. s. BAYLls VPROCESS OF TREATING GRUDE OIL HAVINGr TAR AND ASPHALT CONTENT Filed Nov. 12,. 1927 KQOMU KM .\W

N? www( l WAN Patented Jan. 13, 1931` p UNITED STATES PATENT OFFICE n WALTER BAYLIS, OF ,LOS ANGELES, CALIFORNIA, ASSIGKNOR, BY IME-SNE ASSIGN- MENTS, TO FILTROL COMPANY 0F CALIFORNIA. OF LOS ANGELES, CALIFORNIA, A

CORPORATION OFV CALIFORNIA y .PROCESS F TREATING CR'UDE OIL HAVING TAR AND ASPHALT CONTENT Application led November 12, 1927. `Serial No. 232,738.

My invention relates in particular to petrolcum4 oil processes and it consists ina rocess of treating oil in the production o lubricating oils. Although my invention may be used in connection with the refining of various classes of oils, I shall, for the purpose of illustration, 'describe my invention as used for producing lubricating oil.

I/Vhen crude oil is refined to produce lubrieating. oil, it is usual-ly separated into its various products by fractional distillation or steam reduction so that the cracking and decomposition will be kept as low as possible. 'lhe distillates, cuts, ork stocks derived from the crude oil in the fractional` distillation leave the cylinder stock from which the lu-l bricating oil is produced.

Most of the products obtained by the distillationof crude petroleum oil are not in a marketable condition andr must be .purified or chemically treated to remove resinous mattei-s, hydrocarbons of unsaturated and aromatic groups, and other impurities which givethe products dark colors and unpleasant odors. It is the general practice to purify such products by subjection .to the action of HQSO, and afterward by NaOH which completes the purification and neutralizes any remaining `sulphuric acid. Purifying ,processes o this kind have certain disadvantages. Considerable' acid sludge is formed ranging from five to thirty per` cent in volume which is an appreciable loss. and this se aration takes considerable time. It is an object of this invention toV provide a process of purifying oil which is superior to other processes since it is more rapid in treating the oil, does not have appreciable 40 waste, and does not .f require expensive equipment. l

It is another obJect of this invention to provide a process lin which the oil is distilledl or fractionated, andA purified at the same time.

I have found that oil may be purified bv h 31. Dis osed within the bubble tower 11 is a -mixing it with an-adsorptive material whic absorbs all the impurities from the oil.` This adsorptive material is subsequently filtered from .the oil, thus leaving the oil free from Also this sludge must be separated, p

to provide a process which includes the miX- ing ofoil with'an adsorptive material and then simultaneously subjectin the mixture to the action of a hot va or suc as steam fordistillation purposes. n some grades of oil, I have found it desirable to use avery small percentage of free acid for expediting the purification of the oil. In this case the acid is mixed with the clay before it is added to the oil. lThe acid is thus adsorbed by the clay, no sludge results from the treatment of the oil by the acidified clay, and a later treatment to neutralize the oil is not required.

It is another object of this invention to provide a process which ordinarily requires no separate acid treatment of the oil. Y

' Further objects and advantages will be madeapparent in the following description taken in connectionwith the accompanying drawing in which an apparatus for carrying out the method. of my invention is diagrammatically illustrated.

Referring specifically to the drawin the apparatus of my invention includes a Ila still 10,A a bubble tower 11, an agitator 12, a

pipe still 15, an atmospheric column '16, a cooler 17, a hydraulic pump 18, and a filter press 19.

The batch still 10 is adapted to be charged, as by a pipe 24, drained as by a pipe 25, and heated as by fuel discharged from a burner 26 disposed therebeneath. Connectin the still 10 with the lower portion ofthe bu ble tower 11 is a va or line 27. Opening intothe upper end of t e bubble tower 11 is a refiux pipe 30, and leading from the upper end of t e tower 11 is a gasoline-vapor line series o iloors 32, each of which provides a collecting chamber 33. Leadin from one of these chambers 33 is a pipe 34 t ough which tch ump 13, a series of heat exchangers 14, a.

water-white oil or kerosene is adaptedto be withdrawn from the bubble tower 11. 'Leading from the lower end of the bubble tower 11 and discharging into the agitator 12 is a within the agitator 12 is an agitating rotor 38 which is adapted to be rotated in any suitable manner as by the gears 39. Connecting the lower end of the agitator 12 with the intake of the pump 13 is a pipe 40, while connecting the v.discharge end of the pump 13 with the intake end of the series of heat exchangers 14 is a pipe 41. Connected with the pipe 41 at an elbow thereof is a steam pipe 42 having a valve 43. Connecting the outlet end of the series of heat exchangers 14 with the4 intake end of the pipe still 15 is a pipe 45. The pi e still 15 is heated in any suitable manner as y fuel supplied by a burner 46. The discharge end ofthe still 15 is connected to an intermediate portion of the atmospheric column 16 by a pipe 48. Beneath the point at which the ipe 48 enters the column 16, a series of ba e plates 49 and 50 is dis osed in alternating relation so that any liqui discharged through the pipe 48 into the column 16 must pass in a circuitous route from the point of discharge to the bottom of the colv umn 16.

Arm

D isposed in the atmospheric column 16 above the point at which the pipe 48'connects thereto are pairs 55 of baille plates 49 and 50. These pairs 55 are positioned in spaced relation so as to makev room between adjacent pairs for collector pans 56. Each of the collector pans 56 is connected by a pipe 57 to one of the heat exchangers 14 from which pipes 58 lead to suitableA distillate storage tanks. Leading from the u per end of the atmospheric column 16 is a xed-gas line 60. Connecting the lower end of the atmospheric column 16 to the inlet end of the cooler 17 is a pipe 61. Connecting the discharge end of the cooler 17 to the inlet end of the pump 18 is a pipe 62 into which a solvent pipe 63 connects.l The discharge'end of the pump 18 is connected to the filter The filter ress 19 may be any suita le type of press ut it is preferablyv a Sweetland press. Leading from this press is a liquor discharge pipe 65. he operation 'of the apparatus above described in carrying out the process of my invention is as follows:

As this process is particularly concerned with handling crude oil containing considarable amounts of tar or asphalt, the still 10 is first charged through' the pipe 24 with a suitable quantity of crude oil of this character. The oil is then heated in the stil1'10 so as to drive ofi' the more volatile fractions ofthe oil in the form of .vapors which pass through the vapor line 27 into the bubblepress 19 by a 1pe 64.

tions pass on upward so that gasoline vapors all pass out through the vapor line 31 leading from the upper end of the tower 11. The line 31 leads to any suitable condenser in which the gasoline vapors are condensed.

The only light distillate which is preferablycondensed into a liquid in the tower 11 is water-white oil or gasoline which is drawn 11 and the heavier o f the V oif through the pipe 34. If desired reflux may be admitted through the pipe 30.

The remaining fractions of the vapor which are condensed in the tower 11 are of a heavy character and combine to form what is known as the lubricating cut which passes through the pipe 36 into the agitator 12. As the lubricating cut flows into the agitator 12, an adsorptive agent, which is preferably the vacid-treated clay known as Filtrol but which may be any of the other well known adsorptive clays, is fed into the agitator 12 through the pipe 37. The agitator rotor 38 is rotated constantly so as to mix the lubricating cut of oil and the adsorptive agent. The mixture is drawn from the bottom of the agitator 12 through-thepipe 40 by the pump 13 and discharged through the pipe 41 into the upper end of the series of heat exchangers 14. At this point, the valve 43 may be opened and steam forced into the mixture so 'as to raise the temperature of the mixture and accelerate any adsorptive tendency which the adsorptive agent may have on the lubricating cut as the temperature of the mixture is gradually raised in its passage through the pipe 45 tothe pipe still 15, where it is raised to atemperature of substantially 7 50 F. at which temperature it is ,discharged from the pipe 48 into the atmospheric column 16. The mixture, entering the column 16, flows down through a circuitous path over` the baiiie lates 49 and 50 and releases all of the lighter ractions of the lubricating out so that the residuum whichcollects in the lower end of the column 16 comprises a mixture of fractions which is termed cylinder stock and which has an average density of 26 B.

The various fractions of lubricating cut* which pass upward through the column 16 in the form of ,vapors pare condensed and cooled in the various pans 56, and flowin outward through the heat exchangers 14, e ect a rise of the temperature of the lubricating cut and adsorptive agent mixture as'previously` mentioned. Any fixed gas released in the points, may include the following:

WaX slop B. P. 650o F. Wax distillate B. P. 60091?.- Gas il B. P. 5500-1?. Mineral seal B. P. 500o F The cylinder stock which collects in the lower end of the column 16 :flows through the cooler 17 and the pipe 62 to the pump 18. At this time a suitable solvent is introduced through the pipe 63 into the cylinder stock so that it may be handled more easily bv the Y pump 18 and filter '19. lThe pump 18 forces the diluted cylinder stock through the pipe 64 'into the filter press 19 which retains the ad sorptive clay and permits the purified cylin- .der stock to be discharged through the pipe 65 which conducts it to a suitable place of storage. Whena sufficient amount of cake has been formed in the filter press 19, the flow of mixture through this filter press is stopped and switched to another similar yfilter press held in readiness for this purpose. The cake in the filter press 19 is then washed with a suitable solvent so'as to remove any of the remaining cylinder stock from the cake.

Suitable provision may alsol be made yfor l Cake' Thereafter the lter press is Openedtar and asphalt content which consists in blowing the cake in the press lwith air and steam after removing the retained oil so as to drive out the excess of solvent and dry the and the cake removed and conveyed by any suitable means, such'as a belt conveyor, to the reactivating house where the clay is reactivated so as to a ain be suitable for use in the above describe process. v

When a given charge in the still 10 has been reduced to a residuum consisting mainly of tar and asphalt, this isgdrained to suitable storage throu h the. drain pipe 25 and the still recharge with a fresh supply through the pipe 24..

As stated above, this process has been particularly successful with the use of Filtrol which is a vproduct thathas been chemically treated so that there are no elements therein to cause any chemical reaction when acid is added to it. Therefore, no sulphates are formed as is the case when acid is added to a natural or untreated earth. When Filtrol is used as the adsorptive agent, it is possible to add a slight amount of acid following the reactivating process so that the Flltrol acts as a carrier for the acid in an `unaltered state. Thus, ,due to the enormous surfaces the Filtrol on which the'acid is carried in a thinfilm, there is very powerful action on the oil. even when an extremely small amount of 4 acid has been added to the F1ltr ol.

Another great advantage of using the acid above noted, the submitting of the lubricating cut of oil to the complete fractionating e final .oilproduct is unprocess in the presence of the acidified adsorptive agent purifies the oil by removing asphaltenes and unsaturated hydrocarbons which form in the stills 10 and 15 while the oil is being refined, so that the usual additional purifying step of acid and caustic treatment may be entirely dispensed with.

It is also desired to point out that the impure substances are absorbed by the adsorptive clay befre the vapors are discharged from the mixture of oil and clay in the column 16, so that fractions condensed inthe pans 56 of the column 16 are already purified, and further treatment of these is therefore unvIleCeSSLIy.

A novel and very important feature of my invention is thus seen to be the treatment with an' adsoptive lagent of the ,oil being distilled in both its liquid and vapor iphases. Another novel feature of importance is treating these liquid and vapor phases as they are interchanging with each other by alternate vaporization and condensation. The purification of the various products into which the oil is divided is thus accomplished concurrently with the distillation and with an lefficiency and purity of product hitherto unknown.

'I claim as my invention z.

1. A process of treating crude oil having eliminating the tar and asphalt content by vaporizing' the lighter oil fractions therefrom, fractionally condensing the lubricatsaid mixture sufficiently to vaporize the lighter fractions of said lubricating cut, discharging said heated .mixture into a. fractionating tower wherein the said li hter fractions are vaporized, condensing an withdrawing the evolved vapors, with rawing and cooling the mixture of un-va orized resi ue and clay, and filterin the resldue from the clay toobtain a cylin er stock.

2. A process as defined inclaim 1 in which steam is injected intothe rst mentioned mixture prior to its being heated to fractionating temperature.

3. A process as defined in claim 1 in'which said adsorptive a ent is an adi-treated clay.

4. A process or refining lubricating o il which comprises mixing the oil with adsorbent clay, passing the resultant mixture in a restricted streamthrough a' heating zone and heating. the same therein to a temperature sufficient to vaporize lighter fractions of the lubricating oil, discharging 'the heated nuxby the Filtrol so `that ture into a fractionating zone at a point substantially above the bottom thereof wherein the oil flows downwardly toward the bottom of said fractionatin zone whereby said lightlr fractions are re eased from the mixture andthe released vapors ascend toward the upper portion of said fractionating zone, fractionally condensing said vapors in the portion of said fractionating zone above the `joint of introduction of the heated mixture thereto, separately removing the condensed fractions from said fractionating zone, Withdrawing the mixture of unvaporized lubricating oil and clay from the lower portion of said fractionating zone, and separating the clay from said unvaporized lubricating oil.

5. A process according to claim 4 in which thedadsorbent clay has been activated with acl 6. A process according to claim 4 in which Y the adsorbent'clay has been activated with acid, is free from sulfate salts and carries a small proportion of free acid on its surfaces. 7. A. process according to claim 4, in which the heating occurs in the presence of steam wlliich has been introduced directly into the o In testimon my hand at Ni day of. November, 192'?.

WALTER S BAYLIS.

whereof, I have hereuntoset w York, New York, this 3rd` 

